CN102145268B - Surfactant composition and application of surfactant composition - Google Patents
Surfactant composition and application of surfactant composition Download PDFInfo
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- CN102145268B CN102145268B CN201110022454.5A CN201110022454A CN102145268B CN 102145268 B CN102145268 B CN 102145268B CN 201110022454 A CN201110022454 A CN 201110022454A CN 102145268 B CN102145268 B CN 102145268B
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Abstract
The invention discloses a surfactant composition, which contains: (a) alkoxy carboxylic acid or salt of alkoxy carboxylic acid, having the formula (i), wherein R1 is perfluoroalkyl with 1 to 4 carbon atoms; n is an integer from 1 to 5; Ap is selected from the group consisting of -COO- and -SO3-; M1 is selected from the group consisting of hydrogen, alkaline metal elements and ammonium ions; and (b) perfluorobutyl sulfamide having the formula (ii), wherein R2 is perfluorobutyl; Ap is selected from the group consisting of -COO- and -SO3-; M2 is selected from the group consisting of hydrogen, alkaline metal elements and ammonium ions; and n is an integer from 1 to 5; the weight ratio of the component (a) to the component (b) is 3: 1 to 10:1. The invention also discloses the application of the composition in fluorine-containing monomer polymerization. R1-[CF2O-CF2(CF3)]n-Ap-M1 (i); R2SO2-NH-(CH2)m-NH-COCH=CH-Ap-M2 (ii).
Description
Technical field
The present invention relates to a kind of surface activator composition, this surface activator composition can substitute at present widely used perfluorooctanoic acid salt in fluoropolymer polymer and fluoroelastomer production, is applied to fluoropolymer or elastomer polymerization process.The invention still further relates to the purposes of this surface activator composition in fluoropolymer or elastomer polymerization process.
Background technology
Perfluoro caprylic acid compounds (claim again C8, molecular formula is C7F17COOM, and M is hydrogen, metal cation or ammonium ion) is a kind of artificial synthetic raw material of industry, and it is the general name of perfluoro caprylic acid and derivative thereof.In the perfluoro caprylic acid compounds most widely used general and of greatest concern be exactly perfluorooctanoic acid, it is a kind of basic processing aid (being surfactant) of making the high-performance fluorine-containing polymeric material.Described fluoropolymer is not stained with the consumer goods such as coating and clothes except being widely used in cooker, also is applied in film material for building, chemical pipeline and container, automotive fuel oil system, fire-fighting foams, electronic devices and components and wire cable insulating material, computer chip processor and the system.
On July 8th, 2004, Environmental Protection Agency (EPA) has proposed the suspection of " the Teflon material may be poisonous ", will direct the spearhead of one's attack at the perfluoro caprylic acid compounds.Caused thus domestic and international consumer to the trust crisis of the Teflon product manufactured take the perfluoro caprylic acid compounds as additive, especially in food and related field thereof.
Studies show that the environmental problem root of perfluoro caprylic acid compounds comes from the C8 whole-fluoroalkyl chain segment in this compounds, this whole-fluoroalkyl chain segment can water and oil repellant, has bioaccumulation, extremely difficult the decomposition.In case after being absorbed by organism, its general preferential sticking on the protein, wherein most of plasma protein in blood is combined, and all the other then accumulate in liver and the musculature, are a kind of Some Persistent Organic Pollutants.
A kind of method that solves perfluoro caprylic acid compounds environmental problem is to reduce using and discharging at perfluoro caprylic acid compounds described in the fluoropolymer high performance material production process, thereby progressively reduce the environmental problem of its initiation, but this method can't fundamentally be eliminated the existence of perfluoro caprylic acid compounds in environment.Another kind method is to adopt the substitute of perfluoro caprylic acid compounds, and this method becomes the best approach of present solution perfluoro caprylic acid compounds environmental problem.
For example, the Chinese patent application CN 101535352A that du pont company is submitted to discloses a kind of method that forms the water-borne dispersions of polymer beads, and the polymerizer that the method is used comprises:
(a) number-average molecular weight is at least perfluoroalkyl polyether acid or its salt of 800g/mol, and it contains (CFCF
3-CF
2-O-)
n, (CF
2-CF
2-CF
2-O-)
n, (CF
2-CF
2-O-)
n-(CF
2-O-)
mPerhaps (CF
2-CFCF
3-O-)
n-(CF
2-O-)
mRepetitive; With
(b) at least about the following formula fluorine-containing surfactant of 55 % by weight:
[R
1-O
n-L-A
-]Y
+
Wherein,
R
1It is the aliphatic group of ether-containing key;
N is 0 or 1;
L is the alkylidene of ether-containing key;
A
-Be anionic group;
Y
+Be hydrogen, ammonium or alkali metal cation;
And, R
1-O
nThe chain length of-L-is not more than 6 atoms.
(except suspension polymerisation) perfluorooctanoic acid remains first-selected common agent in the production process of fluorine product at present, no matter is that fluoropolymer polymer or elastomer all can use.And in the research and development of substitute, still do not have a kind of compound can substitute perfluorooctanoic acid fully, be widely used in the polymerization of all fluorine-containing products.Although the disclosed fluorine-containing surfactant of Chinese patent application CN 101535352A that du pont company is submitted to, [R
1-O
n-L-A
-] Y
+, can substantially satisfy the requirement that forms polymer beads, but also have gap apart from the requirement of this area Surfactant, for example, the mechanical stability of the polymer emulsion that makes with this fluorine-containing surfactant also has further room for improvement.
Therefore, this area also needs to develop a kind of surfactant that can replace the perfluoro caprylic acid compounds, the polymer emulsion that forms with this surfactant can have the performance of basic simlarity with the polymer emulsion that forms with the perfluoro caprylic acid compounds, for example, it has gratifying emulsion mechanical stability.
Summary of the invention
Goal of the invention of the present invention is a kind of surfactant that can replace the perfluoro caprylic acid compounds of exploitation.
Therefore, the present invention relates to a kind of surface activator composition, it comprises:
(a) have alkoxyl carboxylic acid or its salt of following general formula (i):
R
1-[CF
2O-CF(CF
3)]
n-Ap-M
1 (i)
Wherein, R
1It is the perfluoroalkyl with 1-4 carbon atom;
N is the integer of 1-5;
Ap is selected from-COO-and-SO
3-;
M
1Be selected from hydrogen ion, alkali metal ion and ammonium ion (NH
+ 4); With
(b) have the perfluoro butyl sulfonamide of following general formula:
R
2SO
2-NH-(CH
2)
m-NH-COCH＝CH-Ap-M
2 (ii)
Wherein, R
2It is perfluoro butyl;
Ap is selected from-COO-and-SO
3-;
M
2Be selected from hydrogen ion, alkali metal ion and ammonium ion (NH
+ 4);
M is the integer of 1-5;
Component (a) and weight ratio (b) are 3: 1-10: 1.
The specific embodiment
The component of surface activator composition of the present invention (a) is alkoxyl carboxylic acid or its salt with following general formula (i):
R
1-[CF
2O-CF(CF
3)]
n-Ap-M
1 (i)
In the alkoxyl carboxylic acid or its salt of general formula (i), R
1Be the perfluoroalkyl with 1-4 carbon atom, better 2 or 3 carbon atoms, its non-limiting example has, for example perfluoro-methyl, perfluor ethyl, perfluor n-pro-pyl, perfluor isopropyl, perfluor normal-butyl, perfluor isobutyl group and the perfluor tert-butyl group; Better be perfluor ethyl and perfluor n-pro-pyl; Perfluor ethyl preferably.
In the alkoxyl carboxylic acid or its salt of general formula (i), n is the integer of 1-5; The integer of 1-3 preferably; The integer of 1-2 more preferably.
In the alkoxyl carboxylic acid or its salt of general formula (i), M
1Be selected from hydrogen ion, alkali metal ion, such as sodium ion, potassium ion, lithium ion etc., and ammonium ion (NH
+ 4); Be preferably M
1Be selected from hydrogen ion, sodium ion, potassium ion and ammonium ion (NH
+ 4); Be more preferably, M is selected from hydrogen ion and ammonium ion (NH
+ 4).
In the alkoxyl carboxylic acid or its salt of general formula (i), Ap is selected from-COO-and-SO
3-.
In a better example of the present invention, alkoxyl carboxylic acid or its salt of general formula (i) are selected from:
In a better example of the present invention, the alkoxyl carboxylic acid of described general formula (i) or the number-average molecular weight of its salt are 200-800g/mol, preferably 300-700g/mol, more preferably 400-600g/mol.
The alkoxyl carboxylic acid or its salt that are applicable to the general formula (i) of surface activator composition of the present invention are commercially available, and for example, it can be buied by Shanghai three Ai Fu companies by the following trade mark:
FS-1：
FS-2:
With
FS-3：CF
3CF
2CF
2OCF(CF
3)SO
3H。
The component of surface activator composition of the present invention (b) is the perfluoro butyl sulfonamide with following general formula (ii):
R
2SO
2-NH-(CH
2)
m-NH-COCH＝CHCOOM
2 (ii)
In the perfluoro butyl sulfonamide of general formula (ii), R
2Perfluoro butyl, for example perfluor normal-butyl, perfluor isobutyl group, the perfluor tert-butyl group.
In the perfluoro butyl sulfonamide of general formula (ii), M
2Be selected from hydrogen ion, alkali metal ion, such as lithium ion, sodium ion, potassium ion etc., and ammonium ion (NH
+ 4), preferably hydrogen ion, sodium ion and ammonium ion (NH
+ 4), more preferably hydrogen ion or ammonium ion (NH
+ 4).
In the perfluoro butyl sulfonamide of general formula (ii), Ap is selected from-COO-and-SO
3-.
M is the integer of 1-5, better is the integer of 1-3, is more preferably the integer of 1-2.
In a better example of the present invention, the perfluoro butyl sulfonamide of described general formula (ii) is n-C
4F
9SO
2NHCH
2CH
2NHCOCH=CHCOONH
4
In a better example of the present invention, the number-average molecular weight of described general formula (ii) perfluoro butyl sulfonamide is 300-600g/mol, preferably 350-550g/mol, more preferably 400-500g/mol.
The perfluoro butyl sulfonamide that is applicable to the general formula (ii) of surface activator composition of the present invention can be buied from the market, and for example, it can be buied by Shanghai Fu Nuolin company.
In the present composition, component (a) and weight ratio (b) are 3: 1-10: 1, preferably 4: 1-8: 1, more preferably 4.5: 1-6: 1.
Under the same conditions, the surface tension value of surface activator composition of the present invention significantly is lower than the surface tension value of perfluoro caprylic acid and salt thereof, thereby can advantageously replace the perfluoro caprylic acid compounds for the preparation of fluoropolymer.For example, weight ratio (a): be that surface tension is low in the water that has under same concentrations and temperature than independent perfluorooctanoic acid of the surface tension in the water that has under 5 ‰ concentration and 23 ℃ of 5: 1 surface activator composition of the present invention (b).
Surface activator composition of the present invention is fit to prepare fluoropolymer by the polymerization fluorinated monomer, the non-limiting example of suitable fluorinated monomer has, for example tetrafluoroethene, hexafluoropropene, CTFE, trifluoro-ethylene, hexafluoro-isobutene, perfluoro alkyl ethylene, fluorinated ethylene base ether, perfluor (allyl vinyl ether) and perfluor (cyclobutenyl vinyl ethers).Preferred fluorinated ethylene base ether comprises perfluor (alkyl vinyl ether) monomer (PAVE), such as perfluor (propyl vinyl ether) (PPVE), perfluor (ethyl vinyl ether) (PEVE) and perfluor (methyl vinyl ether) (PMVE).Nonfluorinated olefinic comonomer such as ethene and propylene can with the fluorinated monomer copolymerization.
The method that polymerization fluorinated monomer of the present invention prepares fluoropolymer can be any fluoropolymer preparation method known in the art, only adopts surface activator composition of the present invention to replace existing perfluorooctanoic acid as surfactant.
Further specify the present invention below by embodiment.
Embodiment
The test of emulsion mechanical stability
At the about 100cm of height, diameter is about in the rustless steel container of 75cm, slowly pouring 300ml left and right sides temperature into is 23 ℃ ± 1 ℃ sample, dispersing head and 0 ℃-100 ℃, calibration are installed are 0.1 ℃ thermometer, respectively dispersing head and thermometer is placed the position of about 2cm at the bottom of the stainless steel cup.The rotating speed of high speed dispersor is transferred to D shelves (19000 rev/mins), and power-on begins high speed dispersion, presses simultaneously manual time-keeping.Behind the high speed dispersion certain hour, sample cohesion, the temperature and time of record sample congealing point.
Embodiment 1
Present embodiment compares the surface tension of perfluorooctanoic acid and surface activator composition of the present invention
(a) sample of preparation component (a)
With following formula: compound:
Be added to the water, (aqueous solution of 25 % by weight, % by weight is pressed NH to add subsequently aqueous ammonium hydroxide
3Calculating), and with electric mixer stir.Add in addition a certain amount of water, so that surfactant concentration is counted 8000ppm by the weight of water.
(b) sample of preparation component (b)
With formula n-C
4F
9SO
2NHCH
2CH
2NHCOCH=CHCOONH
4Perfluoro butyl sulfonamide dilute with water and stir.Add the water of capacity, so that take water as benchmark, surfactant concentration is 8000ppm.
Said sample is mixed into (a): (b) the surface activator composition sample of Different Weight ratio, its visual appearance are transparence, add the water of capacity, so that surfactant concentration is counted 8000ppm by the weight of water.
Use the suspension ring method to carry out surface tension test with SEO-DST30 (Korea S SEO company) tester.The surface tension data are 5 data points average of taking from instrument.Under environment temperature (23 ℃), test.
| Test piece number (Test pc No.) | Form | Ratio | Surface tension |
| 1 | Perfluorooctanoic acid | 28.986 | |
| 2 | Sample (a) | 20.284 | |
| 3 | Surface activator composition | (a)∶(b)＝3∶1 | 24.304 |
| 4 | Surface activator composition | (a)∶(b)＝9∶1 | 22.051 |
By the result of the test of upper table as seen, the surface tension of surface activator composition of the present invention is better than the surface tension of perfluoro caprylic acid and salt thereof under the same conditions.
Comparative example 1
In the vertical response still of 25 liters of outfit blade mixers, add 17500 gram deionized waters, 5.5 gram perfluorooctanoic acids.The closed reaction still vacuumizes and uses nitrogen replacement, until the interior oxygen content of reactor is less than or equal to 10ppm.Then begin to stir with the speed of 500rpm, the reactor internal temperature is risen to 85 ℃, replenish the first copolymerization mix monomer absolute pressure to the reactor and reach 3.0MPa, described the first copolymerization mix monomer mole proportioning is that vinylidene accounts for 44%, tetrafluoroethene accounts for 14%, hexafluoropropene accounts for 42%.Add 2.9 gram sodium peroxydisulfates, the beginning polymerisation.Make by adding the copolymerization mix monomer that absolute pressure maintains 3.0MPa in the reactor, the described copolymerization mix monomer mole proportioning of adding is that vinylidene accounts for 69%, tetrafluoroethene accounts for 16%, hexafluoropropene accounts for 15%.
When the first copolymerization mix monomer consumption reaches 4 kilograms, emit the first copolymerization mix monomer in the reactor, replenish the second copolymerization mix monomer absolute pressure to the reactor and reach 3.0MPa, described the second copolymerization mix monomer mole proportioning is that vinylidene accounts for 48%, tetrafluoroethene accounts for 9%, hexafluoropropene accounts for 43%.Add successively 33.5 gram ethyl acetate, 3.1 gram sodium peroxydisulfates, continue polymerisation.Make by adding the copolymerization mix monomer that absolute pressure maintains 3.0MPa in the reactor, the described copolymerization mix monomer mole proportioning of adding is that vinylidene accounts for 78%, hexafluoropropene accounts for 22%.When the second copolymerization mix monomer consumption reaches 1 kilogram, finish polymerisation.
Use F
19The copolymerization that NMR measures fluoroelastomer forms, and solvent is deuterated acetone, and the copolymerization mole of fluoroelastomer I consists of that vinylidene accounts for 69% as a result, tetrafluoroethene accounts for 16%, hexafluoropropene accounts for 15%.
Press the method estimation of the weight ratio of fluoroelastomer II and fluoroelastomer I=the second copolymerization mix monomer consumption/the first copolymerization mix monomer consumption, the weight ratio of fluoroelastomer II and fluoroelastomer I is 0.25.
Prescription sulfuration shown in the according to the form below 1 obtains the fluoroelastomer vulcanized rubber, measures the performance of the fluoroelastomer that obtains, and the results are shown in table 2.
Embodiment 2
(a) preparation surface activator composition
(i) sample of preparation component (a)
With following formula: compound:
Be added to the water, (aqueous solution of 25 % by weight, % by weight is pressed NH to add subsequently aqueous ammonium hydroxide
3Calculating), and with electric mixer stir.Add in addition a certain amount of water, so that surfactant concentration is counted 8000ppm by the weight of water.
(ii) sample of preparation component (b)
With formula n-C
4F
9SO
2NHCH
2CH
2NHCOCH=CHCOONH
4Perfluoro butyl sulfonamide dilute with water and stir.Add the water of capacity, so that take water as benchmark, surfactant concentration is 8000ppm (weight).
Said sample is mixed into (i): (ii) weight ratio is 9: 1 surface activator composition.
(b) copolymer tetrafluoroethylene (TFE) and vinylidene (VDF)
In the vertical response still of 25 liters of outfit blade mixers, add 17500 gram deionized waters, the above-mentioned surface activator composition of 5.5 grams.The closed reaction still vacuumizes and uses nitrogen replacement, until the interior oxygen content of reactor is less than or equal to 10ppm.Then begin to stir with the speed of 300rpm, the reactor internal temperature is risen to 85 ℃, replenish the first copolymerization mix monomer absolute pressure to the reactor and reach 3.0MPa, described the first copolymerization mix monomer mole proportioning is that vinylidene accounts for 44%, tetrafluoroethene accounts for 14%, hexafluoropropene accounts for 42%.Add 2.9 gram sodium peroxydisulfates, the beginning polymerisation.Make by adding the copolymerization mix monomer that absolute pressure maintains 3.0MPa in the reactor, the described copolymerization mix monomer mole proportioning of adding is that vinylidene accounts for 69%, tetrafluoroethene accounts for 16%, hexafluoropropene accounts for 15%.
When the first copolymerization mix monomer consumption reaches 4 kilograms, emit the first copolymerization mix monomer in the reactor, replenish the second copolymerization mix monomer absolute pressure to the reactor and reach 3.0MPa, described the second copolymerization mix monomer mole proportioning is that vinylidene accounts for 48%, tetrafluoroethene accounts for 9%, hexafluoropropene accounts for 43%.Add successively 33.5 gram ethyl acetate, 3.1 gram sodium peroxydisulfates, continue polymerisation.Make by adding the copolymerization mix monomer that absolute pressure maintains 3.0MPa in the reactor, the described copolymerization mix monomer mole proportioning of adding is that vinylidene accounts for 78%, hexafluoropropene accounts for 22%.When the second copolymerization mix monomer consumption reaches 1 kilogram, finish polymerisation.
Use F
19The copolymerization that NMR measures fluoroelastomer forms, and solvent is deuterated acetone, and the copolymerization mole of fluoroelastomer I consists of that vinylidene accounts for 69% as a result, tetrafluoroethene accounts for 16%, hexafluoropropene accounts for 15%.
The method of pressing the weight ratio of fluoroelastomer II and fluoroelastomer I=the second copolymerization mix monomer consumption/the first copolymerization mix monomer consumption is measured the weight ratio of fluoroelastomer II and fluoroelastomer I, and the result is 0.25.
Obtain the fluoroelastomer vulcanized rubber by the sulfuration of the prescription shown in the table 1, measure the performance of the fluoroelastomer that obtains, the results are shown in table 2.
Embodiment 3
(a) preparation surface activator composition
(i) sample of preparation component (a)
With following formula: compound:
Be added to the water, (aqueous solution of 25 % by weight, % by weight is pressed NH to add subsequently aqueous ammonium hydroxide
3Calculating), and with electric mixer stir.Add in addition a certain amount of water, so that surfactant concentration is counted 8000ppm by the weight of water.
(ii) sample of preparation component (b)
With formula n-C
4F
9SO
2NHCH
2CH
2NHCOCH=CHCOONH
4Perfluoro butyl sulfonamide dilute with water and stir.Add the water of capacity, so that take water as benchmark, surfactant concentration is 8000ppm (weight).
Said sample is mixed into (i): (ii) weight ratio is 4: 1 surface activator composition.
(b) copolymer tetrafluoroethylene (TFE) and vinylidene (VDF)
In the vertical response still of 25 liters of outfit blade mixers, add 17500 gram deionized waters, the above-mentioned surface activator composition of 5.5 grams.The closed reaction still vacuumizes and uses nitrogen replacement, until the interior oxygen content of reactor is less than or equal to 10ppm.Then begin to stir with the speed of 300rpm, the reactor internal temperature is risen to 88 ℃, replenish the first copolymerization mix monomer absolute pressure to the reactor and reach 3.2MPa, described the first copolymerization mix monomer mole proportioning is that vinylidene accounts for 55%, hexafluoropropene accounts for 45%.Add 2.9 gram sodium peroxydisulfates, the beginning polymerisation.Make by adding the copolymerization mix monomer that absolute pressure maintains 3.2MPa in the reactor, the described copolymerization mix monomer mole proportioning of adding is that vinylidene accounts for 78%, hexafluoropropene accounts for 22%.
When the first copolymerization mix monomer consumption reaches 2.5 kilograms, add successively 38.1 gram ethyl acetate, 3.1 gram sodium peroxydisulfates, continue polymerisation.Make by adding the copolymerization mix monomer that absolute pressure maintains 3.0MPa in the reactor, the described copolymerization mix monomer mole proportioning of adding is that vinylidene accounts for 78%, hexafluoropropene accounts for 22%.When the second copolymerization mix monomer consumption reaches 2.5 kilograms, finish polymerisation.
Use F
19The copolymerization that NMR measures fluoroelastomer forms, and solvent is deuterated acetone, and the copolymerization mole of fluoroelastomer I consists of that vinylidene accounts for 78%, hexafluoropropene accounts for 22% as a result.
The method of pressing the weight ratio of fluoroelastomer II and fluoroelastomer I=the second copolymerization mix monomer consumption/the first copolymerization mix monomer consumption is measured the weight ratio of fluoroelastomer II and fluoroelastomer I, and the result is 0.50.
Obtain the fluoroelastomer vulcanized rubber by the sulfuration of the prescription shown in the table 1, measure the performance of the fluoroelastomer that obtains, the results are shown in table 2.
Embodiment 4
(a) preparation surface activator composition
(i) sample of preparation component (a)
With following formula: compound:
With
1: 1 (weight ratio) mixture be added to the water, (aqueous solution of 25 % by weight, % by weight is pressed NH to add subsequently aqueous ammonium hydroxide
3Calculating), and with electric mixer stir.Add in addition a certain amount of water, so that surfactant concentration is counted 8000ppm by the weight of water.
(ii) sample of preparation component (b)
With formula n-C
4F
9SO
2NHCH
2CH
2NHCOCH=CHCOONH
4Perfluoro butyl sulfonamide dilute with water and stir.Add the water of capacity, so that take water as benchmark, surfactant concentration is 8000ppm (weight).
Said sample is mixed into (i): (ii) weight ratio is 9.5: 5 surface activator composition.
(b) copolymer tetrafluoroethylene (TFE) and vinylidene (VDF)
In the vertical response still of 25 liters of outfit blade mixers, add 17500 gram deionized waters, the above-mentioned surface activator composition of 5.5 grams.The closed reaction still vacuumizes and uses nitrogen replacement, until the interior oxygen content of reactor is less than or equal to 10ppm.Then begin to stir with the speed of 300rpm, the reactor internal temperature is risen to 85 ℃, replenish the first copolymerization mix monomer absolute pressure to the reactor and reach 3.0MPa, described the first copolymerization mix monomer mole proportioning is that vinylidene accounts for 44%, tetrafluoroethene accounts for 14%, hexafluoropropene accounts for 42%.Add 2.9 gram sodium peroxydisulfates, the beginning polymerisation.Make by adding the copolymerization mix monomer that absolute pressure maintains 3.0MPa in the reactor, the described copolymerization mix monomer mole proportioning of adding is that vinylidene accounts for 69%, tetrafluoroethene accounts for 16%, hexafluoropropene accounts for 15%.
When the first copolymerization mix monomer consumption reaches 4 kilograms, emit the first copolymerization mix monomer in the reactor, replenish the second copolymerization mix monomer absolute pressure to the reactor and reach 3.0MPa, described the second copolymerization mix monomer mole proportioning is that vinylidene accounts for 48%, tetrafluoroethene accounts for 9%, hexafluoropropene accounts for 43%.Add successively 33.5 gram ethyl acetate, 3.1 gram sodium peroxydisulfates, continue polymerisation.Make by adding the copolymerization mix monomer that absolute pressure maintains 3.0MPa in the reactor, the described copolymerization mix monomer mole proportioning of adding is that vinylidene accounts for 78%, hexafluoropropene accounts for 22%.When the second copolymerization mix monomer consumption reaches 1 kilogram, finish polymerisation.
The mole of measuring fluoroelastomer with said method forms, and the copolymerization mole of fluoroelastomer I consists of that vinylidene accounts for 69% as a result, tetrafluoroethene accounts for 16%, hexafluoropropene accounts for 15%.The weight ratio of fluoroelastomer II and fluoroelastomer I is 0.25.Obtain the fluoroelastomer vulcanized rubber by the sulfuration of the prescription shown in the table 1, measure the performance of the fluoroelastomer that obtains, the results are shown in table 2.
Table 1
| Prescription (weight portion) | Comparative example 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Fluoroelastomer | 100 | 100 | 100 | 100 |
| MT carbon black (N990) | 30 | 30 | 30 | 30 |
| MgO | 3 | 3 | 3 | 3 |
| Ca(OH)2 | 6 | 6 | 6 | 6 |
| Bisphenol AF | 2 | 2 | 2 | 2 |
| BPP | 0.5 | 0.5 | 0.5 | 0.5 |
BPP: benzyl triphenyl phosphonium chloride squama
Table 2
*: the fluoroelastomer emulsion particle diameter is measured with laser light scattering method;
*: the strength character of pressing ASTM D412 standard test fluoroelastomer vulcanized rubber.
Comparative example 2
Perfluoro caprylic acid is added to the water, and (aqueous solution of 25 % by weight, % by weight is pressed NH to add subsequently aqueous ammonium hydroxide
3Calculating), and with electric mixer stir.Add in addition a certain amount of water, so that surfactant concentration is counted 8000ppm by the weight of water.
The polymerization of tetrafluoroethene: in the reactor of 36.24 liters of outfit blade mixers, inject 21.8 liters of deionized waters, the 2g perfluorooctanoic acid, 855g paraffin, after oxygen content is qualified reactor is warming up to 65 ℃, add the 0.33g ammonium persulfate, perfluoro propyl vinyl ether as temperature to 72 ℃ adding 20.5ml is raised to 2.75MPa with still internal pressure tetrafluoroethylene monomer pressure, starts to stir to begin reaction.When 10% tetrafluoroethylene monomer reacts, squeeze into the above-mentioned surfactant mixture of 860ml.
Reaction is reclaimed unreacted tetrafluoroethylene monomer after finishing, and sheds the still internal pressure, obtains solid content and reaches 35% modified Teflon emulsion.Through post processing cohesion, clean, oven dry, obtain modified polytetrafluoroethyldispersion dispersion resin.
Comparative example 3
(i) sample of preparation component (a)
With Compound C F
3CF
2CF
2OCF (CF
3) COOH is added to the water, (aqueous solution of 25 % by weight, % by weight is pressed NH to add subsequently aqueous ammonium hydroxide
3Calculating), and with electric mixer stir.Add in addition a certain amount of water, so that surfactant concentration is counted 8000ppm by the weight of water.
(ii) polymerization of tetrafluoroethene
In 36.24 liters of reactors, inject 21.8 liters of deionized waters, component (a) 2g, paraffin 855g, after oxygen content is qualified reactor is warming up to 65 ℃, add the 0.33g ammonium persulfate, perfluoro propyl vinyl ether as temperature to 72 ℃ adding 20.5ml is raised to 2.75MPa with still internal pressure tetrafluoroethylene monomer pressure, starts to stir to begin reaction.When 10% tetrafluoroethylene monomer reacts, squeeze into the above-mentioned surface activator composition of 860ml.
Reaction is reclaimed unreacted tetrafluoroethylene monomer after finishing, and sheds the still internal pressure, obtains solid content and reaches 35% modified Teflon emulsion.Through post processing cohesion, clean, oven dry, obtain modified polytetrafluoroethyldispersion dispersion resin.
Embodiment 5
(i) sample of preparation component (a)
With Compound C F
3CF
2CF
2OCF (CF
3) SO
3H is added to the water, and (aqueous solution of 25 % by weight, % by weight is pressed NH to add subsequently aqueous ammonium hydroxide
3Calculating), and with electric mixer stir.Add in addition a certain amount of water, so that surfactant concentration is counted 8000ppm by the weight of water.
(ii) sample of preparation component (b)
With formula n-C
4F
9SO
2NHCH
2CH
2NHCOCH=CHCOONH
4Perfluoro butyl sulfonamide dilute with water and stir.Add the water of capacity, so that take water as benchmark, surfactant concentration is 8000ppm (weight).
Said sample is mixed into (i): (ii) weight ratio is 4: 1 surface activator composition.
(iii) polymerization of tetrafluoroethene
In 36.24 liters of reactors, inject 21.8 liters of deionized waters, mixed surfactant 2g, paraffin 855g, after oxygen content is qualified reactor is warming up to 65 ℃, add the 0.33g ammonium persulfate, perfluoro propyl vinyl ether as temperature to 72 ℃ adding 20.5ml is raised to 2.75MPa with still internal pressure tetrafluoroethylene monomer pressure, starts to stir to begin reaction.When 10% tetrafluoroethylene monomer reacts, squeeze into the above-mentioned surface activator composition of 860ml.
Reaction is reclaimed unreacted tetrafluoroethylene monomer after finishing, and sheds the still internal pressure, obtains solid content and reaches 35% modified Teflon emulsion.Through post processing cohesion, clean, oven dry, obtain modified polytetrafluoroethyldispersion dispersion resin.
Embodiment 6
(i) sample of preparation component (a)
With Compound C F
3CF
2CF
2OCF (CF
3) COOH is added to the water, (aqueous solution of 25 % by weight, % by weight is pressed NH to add subsequently aqueous ammonium hydroxide
3Calculating), and with electric mixer stir.Add in addition a certain amount of water, so that surfactant concentration is counted 8000ppm by the weight of water.
(ii) sample of preparation component (b)
With formula n-C
4F
9SO
2NHCH
2CH
2NHCOCH=CHCOONH
4Perfluoro butyl sulfonamide dilute with water and stir.Add the water of capacity, so that take water as benchmark, surfactant concentration is 8000ppm (weight).
Said sample is mixed into (i): (ii) weight ratio is 4: 1 surface activator composition.
(iii) polymerization of tetrafluoroethene
In 36.24 liters of reactors, inject 21.8 liters of deionized waters, mixed surfactant 2g, paraffin 855g, after oxygen content is qualified reactor is warming up to 65 ℃, add the 0.33g ammonium persulfate, perfluoro propyl vinyl ether as temperature to 72 ℃ adding 20.5ml is raised to 2.75MPa with still internal pressure tetrafluoroethylene monomer pressure, starts to stir to begin reaction.When 10% tetrafluoroethylene monomer reacts, squeeze into the above-mentioned surface activator composition of 860ml.
Reaction is reclaimed unreacted tetrafluoroethylene monomer after finishing, and sheds the still internal pressure, obtains solid content and reaches 35% modified Teflon emulsion.Through post processing cohesion, clean, oven dry, obtain modified polytetrafluoroethyldispersion dispersion resin.
Table 3
*: the fluoroelastomer emulsion particle diameter is measured with laser light scattering method;
By above-mentioned result of the test as seen, surface activator composition of the present invention can substitute the perfluoro caprylic acid ammonium surfactant in the homopolymerization of fluoropolymer and/or polymerization process, thus protection of the environment and reduce harm to operating personnel advantageously.In addition, the adding of components b can obviously improve the mechanical stability of polymer emulsion.
Claims (16)
1. surface activator composition, it comprises:
(a) have alkoxyl carboxylic acid or its salt of following general formula (i):
R
1-[CF
2O-CF(CF
3)]
n-Ap-M
1 (i)
Wherein, R
1It is the perfluoroalkyl with 1-4 carbon atom;
N is the integer of 1-5;
Ap is selected from-COO-and-SO
3-;
M
1Be selected from hydrogen ion, alkali metal ion and ammonium ion; With
(b) have the perfluoro butyl sulfonamide of following general formula:
R
2SO
2-NH-(CH
2)
m-NH-COCH=CH-Ap-M
2 (ii)
Wherein, R
2It is perfluoro butyl;
Ap is selected from-COO-and-SO
3-;
M
2Be selected from hydrogen ion, alkali metal ion and ammonium ion;
M is the integer of 1-5;
Component (a) and weight ratio (b) are 3:1-10:1.
2. surface activator composition as claimed in claim 1 is characterized in that in component (a) R
1Be selected from perfluoro-methyl, perfluor ethyl, perfluor n-pro-pyl;
N is the integer of 1-3;
M
1Be selected from hydrogen and ammonium ion;
Ap is selected from-COO-.
3. surface activator composition as claimed in claim 1 or 2 is characterized in that the alkoxyl carboxylic acid of general formula (i) or its salt are selected from:
And the mixture of arbitrary proportion.
4. surface activator composition as claimed in claim 1 or 2 is characterized in that the alkoxyl carboxylic acid of described general formula (i) or the number-average molecular weight of its salt are 200-800g/mol.
5. surface activator composition as claimed in claim 1 or 2 is characterized in that in the perfluoro butyl sulfonamide of general formula (ii) R
2It is the perfluor normal-butyl;
M
2Be selected from hydrogen ion and ammonium ion;
M is the integer of 1-3;
Ap is selected from-COO-.
6. surface activator composition as claimed in claim 1 or 2, the perfluoro butyl sulfonamide that it is characterized in that described general formula (ii) is n-C
4F
9SO
2NHCH
2CH
2NHCOCH=CHCOONH
4
7. surface activator composition as claimed in claim 1 or 2 is characterized in that the number-average molecular weight of described general formula (ii) perfluoro butyl sulfonamide is 300-600g/mol.
8. surface activator composition as claimed in claim 1 or 2 is characterized in that component (a) and weight ratio (b) are 4:1-8:1.
9. surface activator composition as claimed in claim 2 is characterized in that n is the integer of 1-2.
10. surface activator composition as claimed in claim 4 is characterized in that the alkoxyl carboxylic acid of described general formula (i) or the number-average molecular weight of its salt are 300-700g/mol.
11. surface activator composition as claimed in claim 10 is characterized in that the alkoxyl carboxylic acid of described general formula (i) or the number-average molecular weight of its salt are 400-600g/mol.
12. surface activator composition as claimed in claim 5 is characterized in that m is the integer of 1-2.
13. surface activator composition as claimed in claim 7 is characterized in that the number-average molecular weight of described general formula (ii) perfluoro butyl sulfonamide is 350-550g/mol.
14. surface activator composition as claimed in claim 13 is characterized in that the number-average molecular weight of described general formula (ii) perfluoro butyl sulfonamide is 400-500g/mol.
15. surface activator composition as claimed in claim 8 is characterized in that component (a) and weight ratio (b) are 4.5:1-6:1.
16. such as the purposes of each described surface activator composition in the polymerization of fluorochemical monomer among the claim 1-15.
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| CN101535352A (en) * | 2006-11-09 | 2009-09-16 | 纳幕尔杜邦公司 | Aqueous polymerization of fluorinated monomer using polymerization agent comprising fluoropolyether acid or salt and short chain fluorosurfactant |
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| CN101535352A (en) * | 2006-11-09 | 2009-09-16 | 纳幕尔杜邦公司 | Aqueous polymerization of fluorinated monomer using polymerization agent comprising fluoropolyether acid or salt and short chain fluorosurfactant |
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